Marble Production and Environmental Pressure: A Case Study of Hayatabad Industrial Estate Peshawar, Pakistan

doi:10.21203/rs.3.rs-3244303/v1

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Marble Production and Environmental Pressure: A Case Study of Hayatabad Industrial Estate Peshawar, Pakistan

https://doi.org/10.21203/rs.3.rs-3244303/v1

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Background and Objectives:

A gradual growth of the human population has increased the demand for resources, which has put pressure on available natural resources. Industrialization is one of the important sectors to meet human needs. The increasing trend of industrialization is associated with a considerable amount of waste generation which can significantly affect the environment. The marble manufacturing industry is one of the major waste-generating industries that requires special mitigation and environmental assessment to minimize its harmful impacts on the environment.

Methodology:

For this purpose, Hayatabad industrial estate was visited for marble processing plants to know about the mitigation process for marble-waste management. During the fieldwork, 6 marble processing plants were investigated and kept under observation for production to waste management process. To determine the quality of wastewater, samples were also taken at industrial discharge points. The assessment of marble processing plants included the analysis of physical and chemical environmental resources (product and byproduct) generated by the marble industries. To reduce the pollution load, wastewater of the marble industry was treated in the laboratory by adopting physical and chemical treatment methods. The results obtained were compared with the required permissible limits recommended by the Pak-NEQS and WHO.

Results

Findings of the study revealed that the chemical parameters of wastewater were observed above the required limits suggested by the Pak-NEQS/WHO. The noise was also found above the required standards which needs special attention. In terms of water, air and land resources, contamination has been observed through unsafe waste disposal strategies adopted by the marble industries. Results of the chemical treatment (coagulation) with hydrated ferric chloride showed maximum removal of suspended load with 92% efficiency.

Conclusion

It is concluded that marble processing units pose serious threats to the environmental quality by degrading air, water and soil resources. Keeping in view the national standards, these industries need special attention for the waste generation and its safe disposal.

Marble processing plants

wastewater

environmental quality

waste management

waste disposal

The marble processing units have been identified as having significant environmental impacts with a lack of adequate monitoring and control by the authorities concerned.
The practice of safe disposal and recycling of marble sludge was ineffective in all marble processing units which required special attention.
The lack of a sewage treatment plant inside the industrial area allows industries to discharge their effluent/waste directly into nearby water channels, which ultimately affects water quality and the aquatic biota.

Among the natural resources, water is the major component and the key element of life on earth (Trivedi, 1992; Gong et al., 2002). This precious resource is compromised due to the natural and human-made activities e.g., domestic sewage, mining, industrial wastes, and the use of agrochemicals. These activities release toxic metals, inorganic and organic compounds, sediments and pesticides in the water. This leads to a serious deterioration in the quality of freshwater, which in turn leads to freshwater bodies to be altered and changed (Chen et al., 2012). For industries, water is considered important during the manufacturing of the product. In the results, a part of the water is discharged as wastewater, which affects the water quality of receiving water bodies (Azizullah et al., 2011). Consequently, industrial activities are the source of the increase in the level of pollutants in freshwater bodies (Binning and Baird, 2001).

The direct or indirect discharge of the pollutants containing harmful substances into water bodies, without any proper treatment, leads to water pollution, which affects plants and other aquatic organisms. Water pollution has become a major challenge for scientists and researchers around the world (Smedley and Kinniburgh, 2002: Nordstrom, 2002). Previous studies investigating heavy metals in water have now received growing attention because their existence negatively impacts humans, animals and plants (Colic et al., 2010: Hussain et al., 2014). Skin cancer, dermal hyperkeratosis in humans are the most serious effects of drinking polluted water, along with others; neurological, cardiovascular, hematological, respiratory and renal disorders. It also affects the lungs, liver, bladder, and kidneys (Morton and Dunnette, 1994).

In the industrial sector, the marble processing unit is considered the main contributor to wastewater. As marble industries utilize a massive amount of water, therefore, the same quantity of water is generated as wastewater. In Pakistan, particularly in Khyber Pakhtunkhwa, the marble industry is growing day by day. The Khyber Pakhtunkhwa Marble Reserve contributes 97% of the total credits of Marble in Pakistan due to which the province faces a vast ecological implication. Marble industries play an important role in socio-economic development on a global scale but they produce a heavy mass of waste (Ahmad et al., 2019). Two types of waste are produced by marble processing units: solid and semi-liquid or slurry. The large amount of slurry containing water and sufficient marble particles used during mining, processing and polishing steps (Almeida et al., 2007).

Furthermore, millions of tons of industrial waste effluents, produced daily by the marble industries, are dumped into empty pits of sewerage systems, and their accumulation in river beds, streams or lagoons, agricultural and pasture lands without any treatment cause a wide-ranging critical environmental problems (Karasahin and Terzi, 2007, Aukour and Al-Qinna, 2008). After processing, 1-ton marble stone, one ton of slurry is generated which contains 70% (700kg) of water and 30% (300kg) of marble cutting dust and the sludge generated is between 20–30% of the stone weight which is processed (Gazi et al., 2012; Manan and Iqbal, 2007; Dhanapandian et al., 2009). These wastes containing a suspended load of marble processing minerals seriously affect the ecosystem’s flora and fauna and cause hazards to human health, direct or indirect alterations in physico-chemicals parameters of the aquatic ecosystem and may also blocking main channels and drains, ultimately leading to drainage problems (Al-Joulani 2012, Ahmad et al., 2019; Yu et al., 2005).

Nowadays, open and unsafe disposal of marble slurry and sludge into water and soil has become a common practice which is one of the leading environmental concerns (Corinaldesi et al., 2010). To control the pollution from industrial waste, the government of Khyber Pakhtunkhwa has introduced various programs such as Pollution Charge System, Cleaner Production, Self-Monitoring and Reporting, Effluent treatment Plant and established research labs. But none of these has been implemented effectively due to enforcement of poor law (Azizullah et al., 2011).

Besides the great contribution of the stone industry to the global economy, a large amount of waste of different particle sizes and dimensions is generated. Therefore, recycling these wastes and by-products to minimize negative impacts is getting more attention from international organizations and countries (Almeida et al., 2007). Waste recycling has become an important demand by environmental laws in regulation with the concept of sustainable development to achieve eco-friendly, eco-efficient, and workable material. Above all, in recent years, due to an increase in marble used in the building has given rise to the production of marble and ultimately the generation of waste that could not be stored (Demirel and Alyamaç, 2018). This article covers the assessment of marble industries for their manufacturing process, pollution load, waste recycling, and reuse techniques where applicable.

This study was carried out in the industrial zone of Hayatabad, Peshawar, Pakistan. It is one of the famous industrial zones of Khyber Pakhtunkhwa (KP) province having 28 marble processing industries. A total of 23 units are functional. Due to the rich availability of marble stones in the province (KP), the trend of marble processing industries is underway. Such a development has increased the production of industrial effluents. The marble industries generate a heavy load of waste in the form of sewage and sludge. Due to lacking of treatment facilities, the industries discharge their wastes into the nearby water channel and land area which is not environmentally feasible. Previous studies have shown that if industrial effluents are not treated, it can affect the quality of water and soil (Corinaldesi et al., 2010). Effluents from the Hayatabad industrial estate are discharged directly into the main drain called Budni Nala. This nullah falls into the Kabul River, located at a distance of 20 km from the industrial estate. As industrial effluents contain toxic pollutants which deteriorate the water quality of the Kabul River, making it unhealthy for fish, animals, domestic and irrigation purposes (Khan, 2018). To know the situation, few marble industries have been studied in Hayatabad industrial estate for their processing and waste handling techniques if any.

Input

To know the input, six marble processing industries were personally visited. The manufacturing process was observed for a complete cycle. Few open-ended questions were asked from the plant manager and workers about the availability of raw material, production @ per day and type of vehicle for loading.

Output

The output/production of each industry was calculated per day. For this, each industry was monitored during a complete manufacturing cycle (8hrs). As marble stone is the basic raw material, it goes under a series of steps (cutting to polishing) to get a final product. During the production process, waste is generated at each step was observed and quantified.

Air, Noise and Soil quality

The marble processing not only affects water quality but generates unpleasant noise and also adversely affect the air and soil quality. Therefore, all these parameters were observed during the field survey. The sound was monitored for 4–5 times during a complete shift of 8 hours. For this, a sound level meter was used to detect the noise level.

Energy Consumption

To know the consumption rate of energy by the marble processing units, monthly electricity and gas bills were recorded for consumable units. Energy consumption was noted differently for each industry based on their output. For this, the record of electricity bills for the last 3 months was noted for each industry.

Water consumption

The marble processing unit is a water intensive industry. The excessive amount of water is used at various steps of the manufacturing. As a result, a huge quantity of wastewater is generated. Industries were observed for water consumption and wastewater generation rates @ per day.

Waste Management

The industries were observed for waste management. The manager was asked about waste reuse, recycling and disposal.

Physicochemical characteristics of Wastewater

To know the pollution load and the possibilities of recycling, wastewater from marble industries was collected to verify their physicochemical properties. This was important to identify the quality of wastewater and make it suitable for reuse in industries.

Sampling and Chemical Analysis of Wastewater

A total of 18 composite wastewater samples were collected at the discharge points of each industry (3 samples for each industry). Each composite sample consisted of 3 grab samples taken with a difference of 1 hour. Samples were collected in clean, labeled, dried 2-liter plastic bottles. To check the pollution load, samples were analyzed for pH, EC, Turbidity, TSS, TDS and alkalinity by adopting the standard methods for examination of water and wastewater (APHA, 2005). While heavy metals were identified using the method adopted by Bangash et al., 2006 (Table-1).

Table-1: Standard Water Quality Parameters Determination Methods and Instruments

S.No	Parameters	Determination Methods and Instruments	Unit	Reference
1	pH	pH Meter	---	APHA, 2005
2	EC	Conductivity Meter	uS/cm	APHA, 2005
3	TSS, TDS	Gravimetric method, dried at 105^oC	mg/L	APHA, 2005
4	Alkalinity	Titration method, using Phenolphthalein and Methyl Orange indicators	mg/L	APHA, 2005
5	Turbidity	Nephelometric	NTU	APHA, 2005
6	BOD₅	5 days incubation by Reduction of dissolved Oxygen.	mg/L	APHA, 2005
7	COD	Reflux Index	mg/L	APHA, 2005
8	Heavy Metals	Determined by Atomic Absorption Spectrophotometer AAS (700)	mg/L	Bangash, et al, 2006

Treatment of Marble wastewater

To check the possibility of the wastewater being reused by the marble industry, one of the collected samples was tested in the laboratory with physical and chemical methods. Sample#6 named Marble-6 industry was selected for laboratory treatments. First, the physical treatment was performed by the process of sedimentation. In this method, 1 liter of wastewater sample was taken in a graduated cylinder and allowed to stand for 24 hours. In this treatment, no chemical was added. After 24 hours, when the settable particles settled down, the sample was analyzed for its suspended load, turbidity and other parameters.

Next to Sedimentation, the wastewater sample was treated chemically with the coagulation method. In this method, three hydrated coagulants (FeCl₃.6H₂O, Al₂(SO₄)₃.18H₂O and FeSO₄.7H₂O) were applied to the wastewater for the removal of suspended solids. For this, one-liter stock solution of each coagulant was prepared. Different volumes of stock solutions were added to the sample to get the required results. The Jar-Test method was applied by adding coagulants of different doses (10ml to 50ml). The Jar apparatus consisted of 3 cylinders with a capacity of 1 liter each. The sample was shaken well and then transferred into the Jar apparatus. The effect of adding 10-50ml coagulants was tested separately. Coagulant dose and settling time were noted for the efficiency of removing the suspended load. The pollutant removal efficiency was determined by the percentage removal of pollutants.

Statistical Analysis

Statistics including average, standard deviation and ANOVA were applied for data interpretation. The purpose of analysis of variance (one-way ANOVA) was to know the level of significance among different variables using SPSS software with a 95% confidence level.

Percentage Removal Efficiency

The percentage removal of pollutants from wastewater was determined using equation-1.

C₁ refers initial value of pollutants and C2 refers final value of pollutants (Sivakumar and Nouri, 2015).

Raw Material Required by Marble Industries

The marble industry is a small-scale industry. Before 2010, they were observing 2 to 3 shifts per day of 8 hours each. Due to the war on terror, the duty hours were decreased. After 2014 and onwards, the number of shifts has been decreased to one shift with 8 to 12 working hours per day. It has decreased the production rate of industries by 30–40%. Other reasons for reduced working hours and low production are the insecure environment (terrorism) and the lack of skilled labor. Marble stone is used as the basic raw material. It is required in the range 10000–18000 Kg per day by each industry (Table-2). The raw material comes from the regions neighboring Peshawar, including the areas of Mardan, Swabi, Buner and Hazara. It is supplied by the contractors to the industries. Thelarge vehicle (truck, traila) is used to bring the raw material. Water is another important input used in the manufacturing of marble. The daily intake of water consumption is 1700 to 2500 m³ per industry (Table-2). The source of water is groundwater. Each industry has its own source of underground water. Plastic and paper are the minor raw materials required for packing.

Output generated by Marble Industries

The marble processing industry is a resource- intensive and a regular source of pollution. Besides the product, waste is produced that is classified as by-product or waste. The production rate of 6 marble industries is calculated between 8500 to 15500 Kg/day (Table-2.) Waste is generated in the form of gravels and damaged slabs, slurry and sludge, dust, wastewater, oil and lubricants as discussed below;

Solid Waste generated by Marble Industries

As marble stone is the main input of the industry, therefore, it undergoes various steps to make the final product. Table-2 shows the quantity of waste determined for the marble processing industries. In Addition to wastewater, the marble industries also contribute a large part to the production of solid waste in the order of 1500 to 2500 Kg/day. This waste comes in the form of sludge and waste-marbles. The damaged marbles are sold to the community for construction while the sludge is dumped openly on the roadside or in the nearby areas. Marble waste is a good raw-material in the preparation of secondary products. By using it as a raw-material, this will help to protect the environment and would be cost-effective. During the field visit, waste handling and its management was identified as the most serious problem for industries and their environment. But no one intends to launch efforts to alleviate this problem and to hand over the responsibility of managing environmental problems to the government.

On the other hand, the lack of government incentives was also seen as ineffective. Due to the lack of treatment facilities, dumping sites and recycling systems for industrial solid waste, people have to face an unhealthy environment. This mismanagement of solid waste opens a pathway for environmental pollution, posing adverse effects on the environment and humans. Marble slurry is rich in CaCO₃ that affects life and block the main drains and channels thus causing drainage problems (Al-Joulani, 2012). To overcome the environmental problems, Pakistan took the first step in 1983 in the form of Environmental Protection Ordinance (PEPO) with the help of Environmental Protection Agencies (EPAs) to formulate the Pakistan Environmental Protection Act,1997 (PEPA). For all developmental and manufacturing activities, Environmental Protection Assessment (EIA) was considered mandatory under section 12 of PEPA-1997. EPA proposed monitoring rules and IEE/EIA regulations and considered it mandatory for small and large scale industries such as sugar, steel, cement and marble industries etc. As marble processing industry is a large scale industry and it needs at least 10 million budget for its installation, therefore, the EPA developed an environmental checklist (EAC) in 2004 (Shah, 2011). Furthermore, national guidelines and permissible safe limits were formulated for industrial discharges by the Pakistan Environmental Protection Agency under clause (d) of Section (6) of the Pakistan Environmental Protection Ordinance with the approval of the Pakistan Environmental Protection Council. They established the National Environmental Quality Standards (NEQS) in 1993 for the air, water and soil (PEPC,1995: JICA, 2003).

Table-2 Solid Waste Produced by Marble Industries at Hayatabad Industrial Estate

Industry	Raw material consumption (Kg)/day	Waste (Kg)/day	Product (Kg)/day	Water Consumption m³/day	Wastewater m³/day	Energy Utilized kWh/month
Marble-1	10000	1500	8500	37	30	16820
Marble-2	10000	1520	8480	40	33	17211
Marble-3	12000	1540	10460	46	40	20123
Marble-4	13000	1600	11400	51	44	23010
Marble-5	15000	1700	13300	57	52	25213
Marble-6	18000	2500	15500	66	60	27264

Energy Consumption

The main source of energy utilized in the marble industries is the electric source. The consumable energy was estimated from monthly bills. The monthly units of consumable electricity for each industry were noted in the range of 16820 to 23010 kWh (Table-2). A considerable amount of energy is used by the marble industries; therefore, each industry installed its separate transformer of about 200 KVA. It was observed during the investigation that the cutting and polishing steps acquire a greater amount of energy. No fuel-burning practice was observed in any industry which, in turn, can help to minimize the environmental impacts generated form energy consumption sources. While Natural Gas is only used for heating and cooking purposes. The only source of energy in the marble industries is grid-supplied electricity.

Oil and Lubricants

During marble manufacturing, oil and lubricants are produced in cutting units, polisher and wheelbarrows. These wastes are considered as hazardous waste and need proper management. But industries lack such practice and they throw lubricants into the main industrial drain. This practice is a big threat to the aquatic biota of receiving water channels.

Plastic and wood

These are minor waste and used as complementary material, holding and packing of marble. As per day estimation, plastic and wood are produced up to 10–15 kg. It is given free of charge to workers or scavengers for burning purposes.

Dust (Air Pollution): Dust has been found emitting during material handling, cutting and polishing of marbles. It was observed to be deposited 3–4 cm on the land surface. This dust has been considered as the main environmental concern of marble manufacturing. This dust poses harmful effects on soil quality, plant growth, water quality, animal and human health. Marble dust has several industrial uses because it contains a high percentage of fine particles and a low percentage of metal oxides. The literature revealed that the calcareous particles of ultra-fine size can be well recovered and then marketed for numeral industrial applications which employ micronized calcium carbonate. These include: the production of cement, paint, paper, soda, lime, agricultural soil amendment, acid neutralizer for heavy metal sorption and industrial discharges desulphurization of flue gas in electric power stations (Misra & Gupta, 2008: Pincomb & Shapiro, 1994). To avoid the harmful effects of dust, no control strategy as observed. Out of the six marble processing units, only 1 plant was observed with medium wet processing. To minimize pollution at source, the UN Environment Program introduced the idea of Cleaner Production (CP) to Pakistan’s industrial sector in 1994 (Ozbay and Demirer, 2007). It is a preventive technique to reduce harmful impacts on the environment by applying environmental regulations. By adopting such techniques, less harmful pollutants are generated (Frondel et al., 2007). Unfortunately, these practices are not adopted due to poor laws.

Noise: During marble manufacturing, noise was monitored in marble industries. The highest noise was noted at the point of noise source above the safe limit in the range of 92–98 dB (Figure-1). While the lowest noise was measured a distance of 50 meters from the source varied from 33–44 dB (Figure-1). According to Pak-NEQS, the proposed permissible limit of industrial noise is 75–80 dB (PEPC, 1995). This limit has been recommended as a draft on the national standard of noise. This draft has been prepared by Pakistan Environmental Protection Council in 1995 which is not approved yet but is applicable. Based on the results, the loud sound poses harmful effects on the eardrums of workers and the people living nearby the factories. Therefore, industrial colony/residential area should be at least 100 m away from noise creating factories. At present, there are no national standards in Pakistan to prescribe noise limits for the industry. Therefore, the EPA don not take action and thus industries are free and not serious to control it. It is, therefore, important to pass the noise pollution control law and the creation of a high level and unnecessary noise has to be prohibited with strict punishment under the law of PEPO,1983. Literature surveys in Pakistan have revealed noise as the silent killer of humans. This issue is increasing from zone to zone and varied according to emission source (Tajik, 2001: Shaukat, 2002: Irfan, 2002: Mehdi et al, 2002).

Fig-1: Noise generated by Marble industries in dB.

Wastewater Characteristics of Marble Industry

The marble industries generate complex wastes in the form of wastewater and marble slurry. Marble cutting and polishing needs water for cooling purposes. As a result, a huge amount of suspended solids is produced (Fig-2). Analysis of wastewater of marble industries showed a heavy load of suspended solids with the average range of 18575–19930 mg/L. This level is higher than Pak-NEQS (150mg/L) and is a major source of water pollution. The regulatory measures of the NEQS do not allow any industry to discharge effluents with TSS concentrations above the safe limit (150mg/L) into a receiving water channel. Therefore, the marble industries must operate the sedimentation tanks to keep the TSS level low before discharging the effluents into a freshwater body.

Fig-2: Physicochemical parameters of wastewater of marble industries.

Turbidity has been identified as the second factor indicating water pollution in marble wastewaters. The average values were recorded between 340–455 NTU. Water rich in TSS will have higher turbidity and low clarity (Shah, 2011). While other parameters such as pH. EC, Alkalinity, TDS, BOD₅ and COD were within the allowable limits (Fig-2). Analysis of heavy metals showed that all metals were found below their permissible limits (Fig-3).

Fig-3: Concentrations of Heavy metals in wastewater of marble industries.

For water reuse, the effluents can be deposited settling ponds. The water is recirculated for cooling. The resulted sludge, also called marble slurry is discarded (Aukour et al., 2008). After recycling the wastewater for 2–3 times, it cannot be reused and is therefore discharged into a nearby stream/river. The existing mechanism in marble units found ineffective in term of recovering the marble slurry. Wastewater from industries is not monitored properly and is discharged into nearby water channels. These discharges contain toxic pollutants that show their significant responses to the aquatic ecosystem. A great diversity of pollutants leads to several disorders (Shah, 2011).

ANOVA test results showed significant differences for pH, EC, TDS, TSS, BOD₅ and COD. While for heavy metals, the test results of ANOVA were insignificant (Table-3). The manufacturing of marble poses several environmental problems, in particular the quality of the water for safe cutting and shaping steps is of great importance. Therefore, the water used in the marble industry needs to be of good quality without containing suspended load (Domopoulou et al., 2015).

Table 3

**ANOVA Test for Wastewater Parameters of Marble Industry** Dependent Variable: data
Type	Dependent Variables	Sum of Squares	Df	Mean Square	F-value	Sig.
Wastewater Parameters	Between Groups	12670410.006	7	2473902.217	150.328	.001
	Within Groups	3425276.400	102	10428.506
	Total	26170651.370	106	-	-	-
Heavy Metals in wastewater	Between Groups	112.016	7	50.018	128.417	.120
	Within Groups	11.872	130	.127
	Total	166.022	131

Construction of settling tank is mandatory under Environmental Impact Assessment (EIA) regulations 2000. In Hayatabad Industrial Estate, each marble industry has constructed the sedimentation tanks, but most of the them are not operational. Another possibility to construct one big sedimentation tank for all marble processing units.

Another problem in waste management is the improper location of marble processing units. Marble industries are scattered out through whole industrial estate and therefore, need a separate sector to relocate. It will cost a single industry $ 3–4 million to install it in a new location. If industries are brought in one zone, they will throw their discharges into the same drain that will be helpful to collect the sludge from one specific site. Marble waste is rich in calcium carbonate contents and is used as an important raw material in the preparation of cement, washing powder and tiles. Therefore, these industries should be kept in one zone. Furthermore, it is possible to install a combine treatment plant near the marble industries to recycle their wastewater. This will reduce the pollution load of the industrial estate which is economically viable and environmentally friendly. The cement and ceramic industries depend on marble waste and therefore, must be placed near the marble industry.

Treatment of Marble Wastewater

For wastewater utilization, wastewater from the marble industry was treated in the laboratory under two stage treatment techniques, i) sedimentation, ii) coagulation. For this purpose, the wastewater from an industry (marble-6) was selected as given below

Wastewater of Marble Industry after Primary Sedimentation. Selected samples of wastewater from marble industries after primary sedimentation showed a gradual change in the physicochemical characteristics, the average pH being noted as 7.2. The level of suspended solids and turbidity were depressed to 33% and 32% respectively (Table-4). The literature has shown that sedimentation is an effective method for the removal of suspended solids (Thompson et al., 2001: Khan et al., 2016). BOD₅ and COD were depressed up to 19% and 14% respectively. Comparative t-tests for untreated and treated samples under the sedimentation process showed significant differences as < 0.05. In case of multiple comparisons, highly significant differences were observed among pH to EC, TSS, BOD₅ and COD. While BOD₅ was found insignificant to COD (Table-5). Marble sludge after recycling is applicable for use as whitewash, in paint, as a filler in concrete, electric insulator and industrial filters (Industrial Minerals HandyBook, 2002). All of these applications provide valuable options from a waste material. Considerably, the most effectual and widely applicable way is using the waste in civil and mining engineering works. (Siotto et al., 2008). In the literature review Arel (2016) and Shah (2015), the examined studies focused on the waste marble use for replacing cement and its cumulative form in concrete production. In our study, no practice of waste reuse or waste sharing was observed in any industry. They disposed of the waste openly which is a big environmental concern for the industrial area.

Table 4

Sedimentation Test Results for Wastewater of Marble Industry
Parameter		Marble Industry-6
Parameter		Min	Max	Avg	SD	Removal (%)
pH	Before	7.4	8.1	7.8	0.34	--
pH	After	7.1	7.4	7.2	0.11	--
EC uS/Cm	Before	824	912	890	9.01	--
EC uS/Cm	After	752	801	769	4.31	--
Alkalinity mg/L	Before	614	675	644	3.42	--
Alkalinity mg/L	After	477	534	518	2.81	--
Turbidity NTU	Before	411	489	455	3.01	32
Turbidity NTU	After	288	344	310	2.71	32
TDS mg/L	Before	554	605	580	3.12	12
TDS mg/L	After	487	540	512	3.00	12
TSS mg/L	Before	23606	25045	24130	11.02	33
TSS mg/L	After	15855	18002	16236	9.14	33
COD mg/L	Before	90	133	102	2.46	14
COD mg/L	After	74	96	88	2.23	14
BOD₅ mg/L	Before	34.5	62	48.5	1.12	19
BOD₅ mg/L	After	29.5	46.5	39	1.05	19

Table 5 ANOVA Test Results for Sedimentation Treated wastewater Dependent Variable: data

Source	Type II Sum of Squares	Df	Mean Square	F-value	Sig.
Model	64135676.225^a	8	4432122.241	126.346	.000
Parameters	41414234.024	7	6535642.123	233.604	.000
treated/untreated	1530418.346	1	1530417.346	43.446	.000
Error	2305864.764	103	300228.126
Total	47643648.340	112
a. R Squared = .916 (Adjusted R Squared = .932)

Wastewater after Treatment with Coagulation

To remove the suspended load and improve the wastewater quality of marble industries, different coagulants have been applied. The pH was adjusted by keeping it within the permissible limit of Pak-NEQS. In treated samples, the values of electrical conductivity and TDS were observed high due to the addition of coagulants. The average values for removable suspended solids ranged between 68% and 92% after coagulation. The highest removal of suspended load was observed with coagulant FeCl₃.6H₂O (92%) with minimum settling time (22mints). Al₂(SO₄)₃.18H₂O also showed efficient results for the removal of pollution load from marble wastewater with 79% of TSS removal. While the lowest removal of suspended load was observed with FeSO₄.7H₂O (68%), shown in Fig-4. pH is an important indicator for water and therefore, is closely associated with the coagulation process. The pH values remained within the safe limit during treatments of FeCl₃.6H₂O and Al₂(SO₄)₃.18H₂O.

Fig-4: Effects of Coagulants on Removal of TSS.

In case of FeSO₄.7H₂O, the pH turned into acidic as 4 to 5.5. Therefore, the Alumina and Ferric chloride found effective for maximum removal of pollutants resulting in low water turbidity. Turbidity is also an important water parameter which determines the presence of colloidal particles. Water with higher colloidal particles show higher turbidity. The colloidal particles have negative surface charges resulting from repulsion forces that exist between particles. To destabilize these particles, it is important to add cationic chemical reagents such as coagulants. During treatment, a decrease trend of settling time was noted with increasing doses of coagulants due to declining of colloidal particles. During coagulation, small molecules combine to form flocks that settle down because of their weight (Kumar et al., 2011). The physicochemical parameters of untreated and treated water samples were found highly significant to each other (< 0.05). While multiple comparisons of water parameters showed significant associations of pH to EC, TSS and COD.

Settling Time

The effect of settling time was noted for the removal of suspended solids. For sedimentation, the observed time was 24hours. In coagulation, the operating time was dependent on the coagulant dose as the settling time was reduced with increasing dosage of coagulants. The. The minimum removal of suspended solids was obtained with 10ml of coagulants. The other doses were applied as 20, 30, 40, and 50ml. Maximum removal of suspended solids (92%) was observed with 50ml of Ferric chloride. For this, the time observed was 52, 43, 29, and 22 minutes.

Literature revealed that coagulation is one of the efficient treatments for the wastewater of the marble industry. Arsalan et al., (2005) reported that coagulation with Alum (Al₂SO₄)₃) and FeCl₃ were considered capable of maximum removal of turbidity and suspended solids.

Aguilar et al., (2002) explored the effective results of coagulation treatment on wastewater of marble industry and reported that coagulation treatment is important for the removal of suspended materials. Semerjian and Ayoub (2003) investigated that coagulation has got much attention for the maximum, removal of pollutants from the wastewater of the marble industry. The presence of lime and carbonates increase the pH and thus lead to water clarification. Domopoulou et al., (2015) reported the effective results of coagulants (Al₂(SO₄)₃, FeCl₃ and FeSO₄ for the removal of suspended solids from the wastewater of the marble industry. This treatment was very efficient with 92% results. Literature revealed that the wastewater from marble processing industry is possible and profitable.

Correlation Between Wastewater Parameters

The results of Pearson correlation among wastewater parameters showed a strong association between pH and EC (r = 0.801), turbidity (r = 0.814), TSS (r = 0.822), BOD5 (r = 0.836) and COD (r = 0.845). A strong correlation was observed between TSS-BOD₅ (r = 0.851) and TSS-COD (r = 0.860). The correlation between BOD₅-COD was observed as r = 0.614 (Table-6). The strong correlations showed that these parameters are dependent on each other for their high and low levels.

Table-6: Pearson Correlation among Wastewater Parameters.

Parameters	Ph	EC	Alkalinity	Turbidity	TDS	TSS	BOD₅	COD
pH	1
EC	0.801^*	1
Alkalinity	0.743	0.788	1
Turbidity	0.814^*	0.754	0.650	1
TDS	0.806^*	0.812^*	0.756	0.842^*	1
TSS	0.822^**	0.789	0.788	0.850^*	0.829^*	1
BOD	0.836^*	0.765	0.794	0.836^*	0.774	0.805^*	1
COD	0.845^**	0.788	0.782	0.759	0.746	0.822^*	0.644	1

Marble processing units have environmental effects on surface water quality. For this reason, the use of water has been changed to a big extent. The existing sedimentation tanks were found effective in water reuse only but not for marble sludge disposal and recycling. Such types of water reuse systems support end-of-pipe treatment in terms of sedimentation and removal of suspended load. After sedimentation, the sediments are disposed of improperly along the bank of the stream. This not only contributes to water pollution but also degrade the soil quality. For Hayatabad Industrial Estate, the treatment of effluents has become an essential requirement before their discharge into receiving water channels. Industries cannot retain effluents any longer and it has to be discharged within a sensible time. Due to the lack of treatment facilities for industrial effluents, mitigation of this problem is necessary to reduce the pollution load.

Recommendations

Following recommendations are suggested to minimize pollution problems generated by marble processing plants on the environment.

There is a need to make the EIA/monitoring process of industries more precise, effective and sound.
The most appropriate method to reduce pollution is based on the recycling of waste. This will help in savings in economy, energy, resources and will sustainably reduce the waste.
In the marble industry, filter press should be used to separate marble powder form slurry. By doing so, this powder will be able to use as raw material in another industry.
With the introduction of new technologies and waste minimization approaches, it is necessary to reduce aquatic pollution and treat industrial wastewater before discharge. The installation of wastewater treatment plants is the scientific solution to this threat. Therefore, remedial actions should be taken to lower this load from manufacturing industries
Marble dumping sites and treatment plants should be planned near the marble processing units for effective waste recycling.
There is a need to upgrade the existing water re-use systems with recovery of suspended load and recycling for implementation of pollution control.
the extent of practical implementation and theoretical knowledge remained underdeveloped among industries. There is a need to elaborate and standardize methods for quantification of sharing of resources among industries.
The movable industries should be shifted into a more sustainable way where they can handle the environmental challenges.
An effective waste management system should be materialized and an environmental friendly Eco-Industrial cluster should be developed.
To keep the environment clean, the Government should plan a waste treatment plant in the study area to prevent the wastage of recyclable wastes. This will be a hub of raw material supply for wanted industries.

Acknowledgement: Authors are very thankful for the plant managers of marble industries for their valuable time and sharing the required information.

DATA AVAILABILITY: The data is original in nature and has not been submitted to any other journal for publication.

Funding: This work is self-owned and not supported by any funding agency.

Competing Interest: the authors have no relevant financial or non-financial interest to disclose.

Author’s Contribution: All the authors contributed to the study. Dr. Nazish Huma Khan is primary author, supervised by Dr. Mohammad Nafees. Mr. Hasham Akbar and Ali Rehman helped in field survey while Dr. Tooba Saeed and Mr. FazliZuljalal helped in lab analysis.

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Marble Production and Environmental Pressure: A Case Study of Hayatabad Industrial Estate Peshawar, Pakistan

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